Composition for dyeing keratin fibers comprising at least one para-phenylenediamine substituted with a diazacycloheptane radical

ABSTRACT

The subject of the invention is a composition for the oxidation dyeing of keratinous fibers, in particular human hair, comprising an oxidation base of the para-phenylenediamine type, substituted with a diazacycloheptane radical. 
     The invention also relates to the method for dyeing fibers using this composition, and the novel compounds of the type mentioned above.

The subject of the invention is a composition for the oxidation dyeingof keratinous fibres, in particular human hair, comprising an oxidationbase of the para-phenylenediamine type, substituted with adiazacycloheptane radical. The invention also relates to the method fordyeing fibres using this composition, and the novel compounds of thetype mentioned above.

It is known to dye keratinous fibres, and in particular human hair, withdyeing compositions containing oxidation dye precursors, generallycalled oxidation bases, such as ortho- or para-phenylenediamines, ortho-or para-aminophenols and heterocyclic compounds. These oxidation basesare colourless or weakly coloured compounds which, combined withoxidizing products, can give rise, by a process of oxidativecondensation, to coloured compounds.

It is also known that the shades obtained with these oxidation bases canbe varied by combining them with colour modifiers, generally calledcouplers, the latter being chosen in particular from aromaticmeta-diamines, meta-aminophenols, meta-diphenols and certainheterocyclic compounds such as indole compounds.

The variety of the molecules used in oxidation bases and couplers makesit possible to obtain a rich palette of colours.

The so-called “permanent” colour obtained using these oxidation dyesmust moreover meet a number of requirements. Thus, it must be withoutdrawbacks from the toxicological point of view, it must make it possibleto obtain shades in the desired intensity and exhibit good resistance toexternal agents such as light, adverse weather conditions, washing,permanent waving, perspiration and rubbing.

The dyes must also make it possible to cover grey hair, and be the leastselective possible, that is to say make it possible to obtain thesmallest possible differences in colour right along the same keratinousfibre, which may indeed be differently sensitized (i.e. damaged) betweenits tip and its root.

It is already known to use 1,4-diazacycloheptane derivatives for theoxidation dyeing of keratinous fibres. For example, Patent U.S. Pat. No.6,165,230 describes a dyeing composition containing1,4-diazacycloheptane derivatives substituted on both nitrogen atoms ofthe ring by an aminobenzene group which makes it possible to obtainintense colorations.

The aim of the present invention is to provide novel compositions fordyeing keratinous fibres, which do not exhibit the disadvantages ofthose of the prior art. In particular, the aim of the present inventionis to provide compositions which contain dyes which are intense, notvery selective and particularly resistant, while being capable ofgenerating intense colorations in varied shades, in particular in thebasic shades.

This aim is achieved with the present invention whose subject is acomposition for the oxidation dyeing of keratinous fibres comprising anoxidation base of the following formula (I) and/or the correspondingaddition salts:

in which:

-   -   R₁ represents    -   a halogen atom, preferably chlorine or bromine;    -   a linear or branched C₁-C₆ hydrocarbon chain, which is saturated        or which may contain one or more double bonds and/or one or more        triple bonds, which may form a 3- to 6-membered ring, it being        possible for one or more carbon atoms to be replaced by an        oxygen, nitrogen or sulphur atom, by an SO₂ group, or, when the        carbon is terminal, by a halogen atom, preferably a chlorine or        bromine atom; the said radical R₁ not containing a peroxide        bond, or a diazo, nitro or nitroso radical;    -   n is between 0 and 4 inclusive, it being understood that when n        is greater than or equal to 2, then the radicals R₁ may be        identical or different,    -   R₂ represents    -   a hydrogen atom;    -   an alkyl radical which may be unsaturated, unsubstituted or        substituted with one or more carboxyl radicals, alkylcarbonyl        radicals, alkoxycarbonyl radicals, carbamoyl radicals, mono- or        dialkylcarbamoyl radicals, saturated and/or unsaturated,        nitrogen-oxygen- and/or sulphur-containing heterocyclic radicals        containing 4, 5, 6 or 7 atoms;    -   an alkyl radical which may be unsaturated, substituted at the        2-position or more by one or more hydroxyl radicals, alkoxy        radicals, amino radicals, mono- or dialkylamino radicals, thiol        radicals or halogen atoms;    -   an alkylcarbonyl radical;    -   an alkoxycarbonyl radical;    -   a mono- or dialkylcarbamoyl radical;    -   a carbamoyl radical;    -   a radical R₆R₇N—C═NR₅— where R₅, R₆, and R₇ represent hydrogen,        a C₁-C₄ alkyl radical or a hydroxyalkyl radical, preferably R₅        is hydrogen and R₆ and R₇ are chosen from hydrogen or a methyl,    -   R₃ represents    -   a hydrogen atom,    -   an alkyl radical which may be unsaturated;    -   a hydroxyl radical;    -   a hydroxyalkyl radical;    -   an alkoxy radical;    -   an alkoxyalkyl radical;    -   an alkylcarbonyl radical;    -   a hydroxyalkoxyalkyl radical;    -   an amino radical;    -   a monoalkylamino or dialkylamino radical;    -   an aminoalkyl radical, it being possible for the amine to be        mono- or disubstituted with an alkyl, acetyl or hydroxyalkyl        radical;    -   a hydroxy- or aminoalkyl radical;    -   a carboxyl radical;    -   a carboxyalkyl radical;    -   a carbamoyl radical;    -   a carbamoylalkyl radical;    -   an alkoxycarbonyl radical;    -   a mono- or dialkylaminocarbonyl radical;    -   R₄ represents    -   an alkyl radical which may be unsaturated;    -   a hydroxyalkyl radical;    -   an alkoxyalkyl radical;    -   an alkylcarbonyl radical;    -   a hydroxyalkoxyalkyl radical;    -   an aminoalkyl radical, it being possible for the amine to be        mono- or disubstituted with an alkyl, acetyl or hydroxyalkyl        radical;    -   a hydroxy- and aminoalkyl radical;    -   a carboxyl radical;    -   a carboxyalkyl radical;    -   a carbamoyl radical;    -   a carbamoylalkyl radical;    -   an alkoxycarbonyl radical;    -   a mono- or dialkylaminocarbonyl radical;    -   m is between 0 and 4 inclusive, it being understood that when m        is greater than or equal to 2, then the radicals R₄ may be        identical or different.

The compounds of formula (I) are para-phenylenediamines substituted witha substituent of the 1,4-diazacycloheptane type, a substituent alsocalled in the literature 1,4-diazepan.

In the above definitions, the alkyl radicals or groups are linear orbranched and comprise, unless otherwise stated, from 1 to 10 carbonatoms, preferably 1 to 6 carbon atoms. An alkoxy radical is an alkyl-Oradical, the alkyl group being as defined above.

The expression unsaturated alkyl radical is understood to mean an alkylof 2 to 10 carbon atoms and comprising one or more double and/or triplebonds.

A substituted alkyl radical is a mono- or polysubstituted alkyl. Forexample, a hydroxyalkyl or an aminoalkyl is an alkyl which may besubstituted with one or more hydroxyl or amino groups. An alkyl radicalsubstituted at the 2-position or more is an alkyl of formula —CH₂—R, Rbeing a substituted alkyl.

According to the invention, when it is indicated that one or more of thecarbon atoms of the radical R₁ may be replaced by an oxygen, nitrogen orsulphur atom or by an SO₂ group, and/or that the said radical R₁ maycontain one or more double bonds and/or one or more triple bonds, thatmeans that it is possible, by way of example, to carry out the followingconversions:

When n is equal to 0, the benzene ring is NH₂—C₆H₄—N—.

In formula (I), when n is different from zero, the radical R₁ is forexample chosen from a chlorine atom, or a methyl, ethyl, isopropyl,vinyl, allyl, methoxymethyl, hydroxymethyl, 1-carboxymethyl,1-aminomethyl, 2-carboxyethyl, 2-hydroxyethyl, 3-hydroxypropyl,1,2-dihydroxyethyl, 1-hydroxy-2-aminoethyl, 1-amino-2-hydroxyethyl,1,2-diaminoethyl, methoxy, ethoxy, allyloxy or 2-hydroxyethyloxyradical.

When n is defined from zero, R₁ is preferably an alkyl, hydroxyalkyl oraminoalkyl, alkoxy, or hydroxyalkoxy radical. In this case, R₁ may bechosen from a methyl, hydroxymethyl, 2-hydroxyethyl, 1,2-dihydroxyethyl,methoxy or 2-hydroxyethoxy radical, and more preferably a methylradical, a hydroxymethyl radical or a 1,2-dihydroxyethyl radical.

According to a preferred embodiment, the oxidation bases of formula (I)are such that n is equal to 0 or 1.

According to a particular embodiment of the invention, the radical R₂ ischosen from hydrogen, an alkyl radical, an alkyl radical substitutedwith a saturated or unsaturated, nitrogen-, oxygen- and/orsulphur-containing heterocyclic containing 4, 5, 6 or 7 atoms, analkoxycarbonyl radical, an alkyl radical substituted at the 2-positionor more with one or more hydroxyl radicals. In this case, R₂ may bechosen from the 2-hydroxyethyl radical, the 3-(1-pyrrolidinyl)-propylradical, the methyl radical, the acetyl radical, hydrogen, and morepreferably the 2-hydroxyethyl radical, the methyl radical or hydrogen.

According to a particular embodiment of the invention, R₃ is chosen fromhydrogen, an alkyl radical, an alkyl radical substituted with one ormore hydroxyl radicals, an alkyl radical substituted with one or moreamino radicals, or a carboxyl radical. In this case, R₃ may be chosenfrom hydrogen, the hydroxyl radical, the carboxyl radical, the aminoradical, the hydroxymethyl radical, or the aminomethyl radical. Amongthese substituents R₃ more preferably represents a hydrogen atom.

According to a particular embodiment, R₄ is chosen from hydrogen, analkyl radical, an alkyl radical substituted with one or more hydroxylradicals, an alkyl radical substituted with one or more amino radicals,or a carboxyl radical. R₄ preferably represents hydrogen.

The carbon substituted with R₃ or with R₄ may be of the (R) and/or (S)configuration.

The addition salts corresponding to formula (I) may be addition saltswith an acid or addition salts with a base.

Among the oxidation bases of formula (I), the following compounds ortheir addition salts with an acid or a base may be mentioned:

Formula Nomenclature

4-(4-Methyl-[1,4]diazepan-1-yl)phenylamine

4-[1,4]Diazepan-1-yl-phenylamine

4-[4-(3-Pyrrolidin-1-yl-propyl)-[1,4]diazepan-1-yl]phenylamine

2-[4-(4-Amino-phenyl)-[1,4]-diazepan-1-yl]ethanol

1-[4-(4-Amino-phenyl)-[1,4]-diazepan-1-yl]ethanone

4-(4-Amino-phenyl)-[1,4]-diazepane-1-carboxamidine

4-(4-Aminophenyl)-N,N-dimethyl-[1,4]diazepane-1-carboxamidine

1-(4-Amino-phenyl)-4-methyl-[1,4]-diazepan-6-ol

1-(4-Aminophenyl)-4-methyl-[1,4]-diazepan-6-ylamine

1-(4-Aminophenyl-4-(3-pyrrolidin-1-yl-propyl)-[1,4]diazepan-6-ol

1-(4-Aminophenyl)-4-(3-pyrrolidin-1-yl-propyl)-[1,4]diazepan-6-ylamine

1-(4-Aminophenyl)-4-(2-hydroxyethyl)-[1,4]diazepan-6-ol

2-[6-Amino-4-(4-aminophenyl)-[1,4]diazepan-1-yl]ethanol

2-[4-(4-Aminophenyl)-6-hydroxymethyl-[1,4]-diazepan-1-yl]ethanol

2-Methyl-4-(4-methyl-[1,4]-diazepan-1-yl)phenylamine

4-[1,4]Diazepan-1-yl-2-methyl-phenylamine

2-Methyl-4-[4-(3-pyrrolidin-1-yl-propyl)-[1,4]diazepan-1-yl]phenylamine

2-[4-(4-Amino-3-methylphenyl)-[1,4]diazepan-1-yl]ethanol

1-[4-(4-Amino-3-methylphenyl)-[1,4]diazepan-1-yl]ethanone

4-(4-Amino-3-methylphenyl)-[1,4]-diazepane-1-carboxamidine

4-(4-Amino-3-methylphenyl)-N,N-dimethyl-[1,4]-diazepane-1-carboxamidine

1-(4-Amino-3-methylphenyl)-4-methyl-[1,4]-diazepan-6-ol

1-(4-Amino-3-methylphenyl)-4-methyl-[1,4]-diazepan-6-ylamine

1-(4-Amino-3-methylphenyl)-4-(3-pyrrolidin-1-yl-propyl)-[1,4]-diazepan-6-ol

1-(4-Amino-3-methylphenyl)-4-(3-pyrrolidin-1-yl-propyl)-[1,4]-diazepan-6-ylamine

1-(4-Amino-3-methylphenyl)-4-(2-hydroxyethyl)-[1,4]-diazepan-6-ol

2-[6-Amino-4-(4-amino-3-methyl-phenyl)-[1,4]-diazepan-1-yl]ethanol

2-[4-(4-Amino-3-methylphenyl)-6-hydroxymethyl-1,4]diazepan-1-yl]ethanol

Preferably, the oxidation bases of formula (I) are chosen from thefollowing compounds and their addition salts with an acid or a base

-   -   4-(4-Methyl-[1,4]diazepan-1-yl)phenylamine    -   4-[1,4]Diazepan-1-yl-phenylamine    -   4-[4-(3-Pyrrolidin-1-yl-propyl)-[1,4]diazepan-1-yl]phenylamine    -   2-[4-(4-Aminophenyl)-[1,4]diazepan-1-yl]ethanol    -   4-[1,4]Diazepan-1-yl-2-methylphenylamine    -   1-[4-(4-Aminophenyl)-[1,4]diazepan-1-yl]ethanone    -   4-(4-Aminophenyl)-[1,4]diazepane-1-carboxamidine    -   4-(4-Aminophenyl)-N,N-dimethyl-[1,4]diazepane-1-carboxamidine    -   1-(4-Aminophenyl)-4-methyl-[1,4]diazepan-6-ol    -   3-Methyl-4-(4-methyl-[1,4]diazepan-1-yl)phenylamine    -   2-Methyl-4-[4-(3-pyrrolidin-1-yl-propyl)-[1,4]diazepan-1-yl]phenylamine    -   2-[4-(4-Amino-3-methylphenyl)-[1,4]diazepan-1-yl]ethanol    -   1-[4-(4-Amino-3-methylphenyl)-[1,4]diazepan-1-yl]ethanone    -   4-(4-Amino-3-methylphenyl)-[1,4]diazepan-1-carboxamidine    -   4-(4-Amino-3-methylphenyl)-N,N-dimethyl-[1,4]diazepane-1-carboxamidine    -   1-(4-Amino-3-methylphenyl)-4-methyl-[1,4]diazepan-6-ol.

In the composition of the present invention, the oxidation base(s) offormula (I) are generally present in a quantity of between 0.001 and 10%by weight approximately of the total weight of the dyeing composition,and preferably between 0.005 and 6%.

The compounds of the present invention may be obtained by analogy withmethods of preparation described in the literature, see in particularpatent application DE 4 241 532 (AGFA).

The composition of the present invention may additionally comprise oneor more additional oxidation bases. These additional oxidation bases arechosen from the oxidation bases conventionally used in oxidation dyeing,for example para-phenylenediamines, bisphenylalkylenediamines,para-aminophenols, ortho-aminophenols and heterocyclic bases and theiraddition salts.

Among the para-phenylenediamines, there may be mentioned moreparticularly, by way of example, para-phenylenediamine,para-tolylenediamine, 2-chloro-para-phenylenediamine,2,3-dimethyl-para-phenylenediamine, 2,6-dimethyl-para-phenylenediamine,2,6-diethyl-para-phenylenediamine, 2,5-dimethyl-para-phenylenediamine,N,N-dimethyl-para-phenylenediamine, N,N-diethyl-para-phenylenediamine,N,N-dipropyl-para-phenylenediamine, 4-amino-N,N-diethyl-3-methylaniline,N,N-bis(β-hydroxyethyl)-para-phenylenediamine, 4-N,N-bis(β-hydroxyethyl)amino-2-methylaniline,4-N,N-bis(β-hydroxyethyl)amino-2-chloroaniline,2-β-hydroxyethyl-para-phenylenediamine, 2-fluoro-para-phenylenediamine,2-isopropyl-para-phenylenediamine,N-(β-hydroxypropyl)-para-phenylenediamine,2-hydroxymethyl-para-phenylenediamine,N,N-dimethyl-3-methyl-para-phenylenediamine,N,N-(ethyl-β-hydroxyethyl)-para-phenylenediamine,N-(β,γ-dihydroxypropyl)-para-phenylenediamine,N-(4′-aminophenyl)-para-phenylenediamine,N-phenyl-para-phenylenediamine,2-β-hydroxyethyloxy-para-phenylenediamine,2-β-acetylaminoethyloxy-para-phenylenediamine,N-(β-methoxyethyl)-para-phenylenediamine, 4-aminophenylpyrrolidine,2-thienyl-para-phenylenediamine, 2-β-hydroxyethylamino-5-aminotoluene,and their addition salts with an acid.

Among the para-phenylenediamines cited above, there are mostparticularly preferred para-phenylenediamine, para-tolylenediamine,2-isopropyl-para-phenylenediamine,2-β-hydroxyethyl-para-phenylenediamine,2-β-hydroxyethyloxy-para-phenylenediamine,2,6-dimethyl-para-phenylenediamine, 2,6-diethyl-para-phenylenediamine,2,3-dimethyl-para-phenylenediamine,N,N-bis(β-hydroxyethyl)-para-phenylenediamine,2-chloro-para-phenylenediamine,2-β-acetylaminoethyloxy-para-phenylenediamine, and their addition saltswith an acid.

Among the bisphenylalkylenediamines, there may be mentioned moreparticularly, by way of example,N,N′-bis(β-hydroxyethyl)-N,N′-bis(4′-aminophenyl)-1,3-diaminopropanol,N,N′-bis(β-hydroxyethyl)-N,N′-bis(4′-aminophenyl)ethylenediamine,N,N′-bis(4-amino-phenyl)tetramethylenediamine,N,N′-bis(β-hydroxyethyl)-N,N′-bis(4-aminophenyl)tetramethylenediamine,N,N′-bis(4-methylaminophenyl)tetramethylenediamine,N,N′-bis(ethyl)-N,N′-bis(4′-amino-3′-methylphenyl)ethylene-diamine,1,8-bis(2,5-diaminophenoxy)-3,5-dioxaoctane, and their addition saltswith an acid.

Among the para-aminophenols, there may be mentioned more particularly,by way of example, para-aminophenol, 4-amino-3-methylphenol,4-amino-3-fluoro-phenol, 4-amino-3-hydroxymethylphenol,4-amino-2-methylphenol, 4-amino-2-hydroxymethylphenol,4-amino-2-methoxymethylphenol, 4-amino-2-aminomethylphenol,4-amino-2-(β-hydroxyethylaminomethyl)phenol, 4-amino-2-fluorophenol, andtheir addition salts with an acid.

Among the ortho-aminophenols, there may be mentioned more particularly,by way of example, 2-aminophenol, 2-amino-5-methylphenol,2-amino-6-methylphenol, 5-acetamido-2-aminophenol and their additionsalts with an acid.

Among the heterocyclic bases, there may be mentioned more particularly,by way of example, the pyridine derivatives, the pyrimidine derivativesand the pyrazole derivatives.

Among the pyridine derivatives, there may be mentioned more particularlythe compounds described for example in Patents GB 1,026,978 and GB1,153,196, such as 2,5-diaminopyridine,2-(4-methoxyphenyl)amino-3-aminopyridine, 2,3-diamino-6-methoxypyridine,2-(β-methoxyethyl)amino-3-amino-6-methoxypyridine, 3,4-diaminopyridine,and their addition salts with an acid.

Among the pyrimidine derivatives, there may be mentioned moreparticularly the compounds described for example in German Patent DE2,359,399 or in Japanese Patents JP 88-169,571 and JP 05 163 124, inEuropean Patent EP 0 770 375 or Patent Application WO 96/15765, such as2,4,5,6-tetraaminopyrimidine, 4-hydroxy-2,5,6-triaminopyrimidine,2-hydroxy-4,5,6-triaminopyrimidine, 2,4-dihydroxy-5,6-diaminopyrimidine,2,5,6-triaminopyrimidine, and the pyrazolopyrimidine derivatives such asthose mentioned in Patent Application FR-A-2,750,048 and among whichthere may be mentioned pyrazolo[1,5-a]pyrimidine-3,7-diamine;2,5-dimethylpyrazolo[1,5-a]pyrimidine-3,7-diamine;pyrazolo[1,5-a]pyrimidine-3,5-diamine;2,7-dimethylpyrazolo[1,5-a]pyrimidine-3,5-diamine;3-aminopyrazolo[1,5-a]pyrimidin-7-ol;3-aminopyrazolo[1,5-a]pyrimidin-5-ol;2-(3-amino-pyrazolo[1,5-a]pyrimidin-7-ylamino)ethanol,2-(7-aminopyrazolo[1,5-a]pyrimidin-3-ylamino)ethanol,2-[(3-aminopyrazolo[1,5-a]pyrimidin-7-yl)-(2-hydroxyethyl)-amino]ethanol,2-[(7-aminopyrazolo[1,5-a]pyrimidin-3-yl)-(2-hydroxyethyl)amino]ethanol,5,6-dimethyl-pyrazolo[1,5-a]pyrimidine-3,7-diamine,2,6-dimethyl-pyrazole[1,5-a]pyrimidine-3,7-diamine, 2,5, N7,N7-tetramethylpyrazolo [1,5-a]pyrimidine-3,7-diamine,3-amino-5-methyl-7-imidazolylpropylaminopyrazolo-[1,5-a]pyrimidine,their tautomeric forms, when a tautomeric equilibrium exists, and theiraddition salts with an acid.

Among the pyrazole derivatives, there may be mentioned more particularlythe compounds described in Patents DE 3,843,892, DE 4,133,957 and PatentApplications WO 94/08969, WO 94/08970, FR-A-2,733,749 and DE-195 43 988such as 4,5-diamino-1-methylpyrazole,4,5-diamino-1-(β-hydroxyethyl)pyrazole, 3,4-diaminopyrazole,4,5-diamino-1-(4′-chlorobenzyl)-pyrazole,4,5-diamino-1,3-dimethylpyrazole, 4,5-diamino-3-methyl-1-phenylpyrazole,4,5-diamino-1-methyl-3-phenylpyrazole,4-amino-1,3-dimethyl-5-hydrazinopyrazole,1-benzyl-4,5-diamino-3-methyl-pyrazole,4,5-diamino-3-tert-butyl-1-methylpyrazole,4,5-diamino-1-tert-butyl-3-methylpyrazole,4,5-diamino-1-(β-hydroxyethyl)-3-methylpyrazole,4,5-diamino-1-ethyl-3-methylpyrazole,4,5-diamino-1-ethyl-3-(4′-methoxyphenyl)pyrazole,4,5-diamino-1-ethyl-3-hydroxy-methylpyrazole,4,5-diamino-3-hydroxymethyl-1-methyl-pyrazole,4,5-diamino-3-hydroxymethyl-1-isopropyl-pyrazole,4,5-diamino-3-methyl-1-isopropylpyrazole,4-amino-5-(2′-aminoethyl)amino-1,3-dimethylpyrazole,3,4,5-triaminopyrazole, 1-methyl-3,4,5-triamino-pyrazole,3,5-diamino-1-methyl-4-methylaminopyrazole,3,5-diamino-4-(β-hydroxyethyl)amino-1-methylpyrazole, and their additionsalts with an acid.

The additional oxidation bases are generally present in a quantity ofbetween 0.001 to 10% by weight approximately of the total weight of thedyeing composition, and preferably from 0.005 to 6%.

The composition according to the invention may contain one or moreconventional couplers used for dyeing keratinous fibres. Among thesecouplers, there may be mentioned in particular meta-phenylenediamines,meta-aminophenols, meta-diphenols, naphthalene couplers and heterocycliccouplers and their addition salts.

By way of example, there may be mentioned 2-methyl-5-aminophenol,5-N-(β-hydroxyethyl)amino-2-methylphenol,6-chloro-2-methyl-5-aminophenol, 3-aminophenol, 1,3-dihydroxybenzene,1,3-dihydroxy-2-methylbenzene, 4-chloro-1,3-dihydroxybenzene,2,4-diamino-1-(β-hydroxyethyloxy)benzene,2-amino-4-(β-hydroxyethylamino)-1-methoxybenzene, 1,3-diaminobenzene,1,3-bis(2,4-diaminophenoxy)propane, 3-ureidoaniline,3-ureido-1-dimethylaminobenzene, sesamol,1-β-hydroxyethylamino-3,4-methylenedioxybenzene, α-naphthol,2-methyl-1-naphthol, 6-hydroxyindole, 4-hydroxyindole,4-hydroxy-N-methylindole, 2-amino-3-hydoxypyridine,6-hydroxy-benzomorpholine, 3,5-diamino-2,6-dimethoxypyridine,1N-(β-hydroxyethyl)amino-3,4-methylenedioxybenzene,2,6-bis(β-hydroxyethylamino)toluene, and their addition salts with anacid.

In the composition of the present invention, the coupler(s) aregenerally present in a quantity of between 0.001 and 10% by weightapproximately of the total weight of the dyeing composition, andpreferably from 0.005 to 6%.

In general, the addition salts with an acid which can be used in thecontext of the dyeing compositions of the invention for the oxidationbases of formula (I), the additional oxidation bases and the couplersare chosen in particular from hydrochlorides, hydrobromides, sulphates,citrates, succinates, tartrates, lactates, tosylates,benzenesulphonates, phosphates and acetates.

The addition salts with a base which can be used in the context of theinvention are chosen for example from the addition salts with sodiumhydroxide, potassium hydroxide, ammonium hydroxide, amines andalkanolamines.

The dyeing composition in accordance with the invention may additionallycontain one or more direct dyes which may be chosen in particular fromnitro dyes of the benzene series, cationic direct dyes, azo direct dyes,methene direct dyes.

The medium appropriate for dyeing also called dye carrier generallyconsists of water or of a mixture of water and of at least one organicsolvent to solubilize the compounds which might not be sufficientlysoluble in water. As organic solvent, there may be mentioned for examplelower C₁-C₄ alkanols, such as ethanol and isopropanol; polyols or polyolethers such as 2-butoxyethanol, propylene glycol, monomethyl ether ofpropylene glycol, monoethyl ether and monomethyl ether of diethyleneglycol, as well as aromatic alcohols such as benzyl alcohol orphenoxyethanol, and mixtures thereof.

The solvents may be present in proportions preferably of between 1 and40% by weight approximately relative to the total weight of the dyeingcomposition, and still more preferably between 5 and 30% by weightapproximately.

The dyeing composition in accordance with the invention may also containvarious adjuvants which are conventionally used in hair-dyeingcompositions, such as anionic, cationic, nonionic, amphoteric orzwitterionic surfactants or mixtures thereof, anionic, cationic,nonionic, amphoteric or zwitterionic polymers or mixtures thereof,inorganic or organic thickening agents, and in particular anionic,cationic, nonionic and amphoteric polymeric associative thickeners,antioxidants, penetrating agents, sequestering agents, perfumes,buffers, dispersing agents, conditioning agents such as for examplemodified or unmodified, volatile or nonvolatile silicones, film-formingagents, ceramides, preservatives and opacifying agents.

These above adjuvants are generally present in a quantity for each ofthem of between 0.01 and 20% by weight relative to the weight of thecomposition.

Of course, persons skilled in the art will be careful to choose this orthese possible additional compounds such that the advantageousproperties intrinsically attached to the oxidation dyeing composition inaccordance with the invention are not, or not substantially, impaired bythe addition(s) envisaged.

The pH of the dyeing composition in accordance with the invention isgenerally between 3 and 12 approximately, and preferably between 5 and11 approximately. It can be adjusted to the desired value by means ofacidifying or alkalinizing agents normally used in dyeing keratinousfibres or using conventional buffer systems.

Among the acidifying agents, there may be mentioned, by way of example,inorganic or organic acids such as hydrochloric acid, orthophosphoricacid, sulphuric acid, carboxylic acids such as acetic acid, tartaricacid, citric acid, lactic acid and sulphonic acids.

Among the alkalinizing agents, there may be mentioned, by way ofexample, aqueous ammonia, alkali metal carbonates, alkanolamines such asmono-, di- and triethanolamines as well as derivatives thereof, sodiumor potassium hydroxides and the compounds of the following formula(III):

in which W is a propylene residue optionally substituted by a hydroxylgroup or a C₁-C₄ alkyl radical; R₆, R₇, R₈ and R₉, which are identicalor different, represent a hydrogen atom, a C₁-C₄ alkyl or C₁-C₄hydroxyalkyl radical.

The dyeing composition according to the invention may be provided invarious forms, such as in the form of liquids, creams, gels or in anyother form appropriate for carrying out a dyeing of keratinous fibres,and in particular human hair.

The subject of the invention is also a method of dyeing keratinousfibres, and in particular human keratinous fibres such as hair, usingthe dyeing composition as defined above.

According to this method, the composition according to the presentinvention is applied to the fibres, the colour being developed with theaid of an oxidizing agent. The colour may be developed at an acidic,neutral or alkaline pH and the oxidizing agent may be added to thecomposition of the invention just at the time of use or it may be usedfrom an oxidizing composition containing it, applied simultaneously orsequentially to the composition of the invention.

According to a particular embodiment, the composition according to thepresent invention is mixed, preferably at the time of use, with acomposition containing, in a medium appropriate for dyeing, at least oneoxidizing agent, this oxidizing agent being present in a sufficientquantity to develop a colour. The mixture obtained is then applied tothe keratinous fibres. After an exposure time of 3 to 50 minutesapproximately, preferably 5 to 30 minutes approximately, the keratinousfibres are rinsed, washed with shampoo, rinsed again and then dried.

The oxidizing agents conventionally used for the oxidation dyeing ofkeratinous fibres are for example hydrogen peroxide, urea peroxide,alkali metal bromates, persalts such as perborates and persulphates,peracids and oxidase enzymes among which there may be mentionedperoxidases, oxidoreductases containing two electrons such as uricasesand oxygenases containing 4 electrons such as laccases. Hydrogenperoxide is particularly preferred.

The oxidizing composition may also contain various adjuvantsconventionally used in hair dyeing compositions and as defined above forthe composition of the invention.

The pH of the oxidizing composition containing the oxidizing agent issuch that after mixing with the dyeing composition, the pH of theresulting composition applied to the keratinous fibres varies between 3and 12 approximately, and preferably between 5 and 11. It can beadjusted to the desired value by means of acidifying or alkalinizingagents normally used for dyeing keratinous fibres and as defined above.

The composition which is finally applied to the keratinous fibres may beprovided in various forms, such as in the form of liquids, creams, gels,or in any other form appropriate for dyeing keratinous fibres, and inparticular human hair.

Another subject of the invention is a multicompartment device or dyeing“kit” in which a first compartment contains the dyeing compositiondefined above and a second compartment contains the oxidizingcomposition. This device may be equipped with a means which makes itpossible to deliver the desired mixture onto the hair, such as thedevices described in patent FR-2 586 913 in the name of the applicant.

Finally, the subject of the invention is also the coloured product whichcan be obtained by oxidative condensation of the composition of thepresent invention. This composition comprises at least one oxidationbase of formula (I) as defined above in the presence of at least oneoxidizing agent as defined above and optionally in the presence of atleast one coupler and/or at least one additional oxidation base.

These coloured products may be provided in particular in the form ofpigments and may be used as direct dyes for the direct dyeing of hair ormay be incorporated into cosmetic products such as for example intomakeup products.

The subject of the present invention is finally the novelpara-phenylenediamine derivatives of formula (I) with the exception of4-(4-methyl-[1,4]diazepan-1-yl)phenylamine.

The examples which follow serve to illustrate the invention withouthowever exhibiting a limiting character.

EXAMPLES Example 1 Synthesis of4-(4-methyl-[1,4]diazepan-1-yl)phenylamine dihydrochloride (2)

Step 1: Synthesis of 1-methyl-4-(4-nitrophenyl)-[1,4]diazepane (1)

Fluoronitrobenzene (10.3 g, 0.073 mol) is dissolved in water and thenpotassium carbonate (12.1 g, 0.0876 mol) is added.1-Methyl[1,4]diazepane (10 g, 0.0876 mol) is introduced and then thereaction medium is heated under reflux (≅100° C.) for 5 hours. Themedium is cooled. A precipitate forms, which is filtered and washed withwater. A yellow solid is recovered, which is dried at 45° C. in a vacuumoven (16.21 g, yield=94.5%).

Spectroscopic Data:

¹H NMR (DMSO d6, 200 MHz): 1.63-1.75 (m, 2H), 2.06 (s, 3H), 2.22-2.33(m, 2H), 2.40-2.45 (m, 2H), 3.34-3.51 (m, 4H), 6.58-6.66 (m, 2H),7.79-7.88 (m, 2H)

Step 2: Synthesis of 4-(4-methyl-[1,4]diazepan-1-yl)phenylamine,dihydrochloride (2)

In a stainless steel hydrogenating reactor, 6 g of1-methyl-4-(4-nitrophenyl)-[1,4]diazepane (1) (25.5 mmol) are partiallydissolved in 300 ml of ethanol. 2.1 g of 5% Pd/C (50% moist) are added,the reactor is closed and purged with nitrogen 3 times, with stirring(1800 rpm). Hydrogen is then introduced at a pressure of 12 bar at roomtemperature for 4 hours. The reactor is then purged with nitrogen andthe reaction medium is filtered under a nitrogen atmosphere and thefiltrate is immediately recovered in a solution containing 9.6 ml of 37%hydrochloric acid and 50 ml of isopropanol. The filtrate is thenconcentrated until a precipitate is obtained. The solid is filtered,washed with isopropanol and then dried under vacuum in the presence ofpotassium hydroxide. 4.5 g (63%) of4-(4-methyl-[1,4]diazepan-1-yl)phenylamine, dihydrochloride (2) are thusobtained in the form of a white solid.

Spectroscopic Data:

¹H NMR (D20 d6, 400 MHz): 2.16 (m, 1H), 2.35 (m, 1H), 2.77 (s, 3H),3.08-3.15 (m, 2H), 3.38-3.46 (m, 4H), 3.73-3.80 (m, 2H), 6.82 (d, J=9.2Hz, 2H), 7.21 (d, J=9.2 Hz, 2H)

¹³C NMR (MeOD, 100 MHz): 23.3, 43.05, 43.44, 46.85, 54.90, 55.88

Mass spectrum: spectrum in conformity with the structure.

Example 2 Synthesis of 4-[1,4]diazepan-1-yl-2-methylphenylamine,dihydrochloride (3)

Step 1: Synthesis of 1-(3-methyl-4-nitrophenyl)-[1,4]diazepane (1)

Fluoronitrobenzene (9.1 g, 0.0586 mol) is dissolved in water (50 ml) andthen potassium carbonate (9.7 9, 0.0703 mol) and 1-acetyl-[1,4]diazepane(10 g, 0.0703 mol) are added. The medium is heated at 95° C. for 6hours, and an orange-coloured solution is obtained. The medium is thencooled to room temperature, and an orange-coloured sticky paste thenappears. The maximum amount of water is removed from the reactionmedium. Isopropanol is then added to the paste until a yellow solidprecipitates. The medium is filtered and, after drying in a vacuum ovenat 45° C., a yellow powder is obtained which corresponds to1-(3-methyl-4-nitrophenyl)-[1,4]diazepane (1). (8.7 g; Yield=53.6%)

Spectroscopic Data:

¹H NMR (DMSO d6, 200 MHz): 1.57-1.81 (m, 5H), 2.39 (s, 3H), 3.13-3.25(m, 4H), 3.38-3.52 (m, 5H), 3.60-3.65 (m, 1H), 6.56-6.63 (m, 2H),7.79-7.85 (m, 1H)

Step 2: Synthesis of 1-(3-methyl-4-nitrophenyl)-[1,4]diazepane (2)

1-(3-Methyl-4-nitrophenyl)-[1,4]diazepane 1 (8 g, 0.0289 mol) issuspended in a 37% HCl solution (29 ml) in water (145 ml). The medium isheated under reflux (100° C.) for 30 hours. It is allowed to cool, and abrown precipitate is then obtained. About 30 ml of 35% sodium hydroxideare added to pH=7. The reaction medium is then concentrated until asolid appears. After filtration, this solid is recrystallized from anisopropanol/methanol mixture. A brown powder is thus obtained whichcorresponds to 1-(3-methyl-4-nitrophenyl)-[1,4]diazepane (2). (2.4 g,Yield=33%)

Spectroscopic Data:

¹H NMR (DMSO d6, 200 MHz): 2.18 (m, 2H), 2.65 (s, 3H), 3.12-3.14 (m,2H), 3.25 (m, 2H), 3.70-3.76 (m, 2H), 3.92 (m, 2H), 6.84 (m, 2H),8.02-8.12 (m, 1H), 9.03-9.33 (m, 1H)

Step 3: Synthesis of 4-[1,4]diazepan-1-yl-2-methylphenylamine,dihydrochloride (3)

In a stainless steel hydrogenating reactor, 2.34 g of1-(3-methyl-4-nitrophenyl)-[1,4]diazepane 2 (9.96 mmol) are dissolved in150 ml of ethanol. 1.2 g of 5% Pd/C (50% moist) are added, the reactoris closed and purged with nitrogen 3 times, with stirring (1800 rpm).Hydrogen is then introduced at a pressure of 9 bar at room temperaturefor 3 hours. The reactor is then purged with nitrogen and the reactionmedium is filtered under a nitrogen atmosphere and the filtrate isimmediately recovered in a solution containing 3.7 ml of 37%hydrochloric acid and 16 ml of isopropanol. The filtrate is thenconcentrated until a precipitate is obtained. The solid is filtered,washed with isopropanol and then dried under vacuum in the presence ofpotassium hydroxide. 2 g (72%) of4-[1,4]diazepan-1-yl)-2-methylphenylamine, dihydrochloride (3) are thusobtained in the form of a white solid.

Spectroscopic Data:

¹H NMR (D20 d6, 400 MHz): 1.92-1.99 (m, 2H), 2.09 (m, 3H), 3.03-3.09 (m,2H), 3.18-3.23 (m, 2H), 3.36-3.40 (m, 2H), 3.56-3.61 (m, 2H), 6.59-6.60(m, 2H), 7.00 (d, J=8.7 Hz, 1H)

Mass spectrum: spectrum in conformity

Example 3 Synthesis of4-[4-(3-pyrrolidin-1-yl-propyl)-[1,4]diazepan-1-yl)phenylamine,trihydrochloride (2)

Step 1: Synthesis of1-(4-nitrophenyl)-4-(3-pyrrolidin-1-yl-propyl)-[1,4]diazepane (1)

Fluoronitrobenzene (5.56 g, 39.43 mmol) is dissolved in water, and thenpotassium carbonate (6.55 g, 47.31 mmol) and1-(3-pyrrolidinopropyl)-homopiperazine (10 g, 47.31 mmol) are added. Themedium is heated at 85° for 4 hours and then cooled to room temperature.The medium is filtered and a yellow solid is recovered after drying in avacuum oven at 45° C. (12.5 g, yield=95.5%).

Spectroscopic Data

¹H NMR (DMSO d6, 200 MHz): 1.55-1.71 (m, 6H), 1.90-1.96 (m, 2H),2.32-2.61 (m, 10H), 2.75-2.80 (m, 2H), 3.63-3.73 (m, 4H), 6.89 (d, J=9.4Hz, 2H), 8.09 (d, J=9.4 Hz, 2H)

Step 2: Synthesis of4-[4-(3-pyrrolidin-1-yl-propyl)-[1,4]diazepan-1-yl]phenylamine,trihydrochloride (2)

In a stainless steel hydrogenating reactor, 6.6 g of1-(4-nitrophenyl)-4-(3-pyrrolidin-1-yl-propyl)-[1,4]diazepane (1) (19.9mmol) are partially dissolved in 300 ml of ethanol. 2.3 g of 5% Pd/C(50% moist) are added, the reactor is closed and purged with nitrogen 3times, with stirring (1800 rpm). Hydrogen is then introduced at apressure of 10 bar at room temperature for 3 hours. The reactor is thenpurged with nitrogen and the reaction medium is filtered under anitrogen atmosphere and the filtrate is immediately recovered in asolution containing 9.1 ml of 37% hydrochloric acid and 40 ml ofisopropanol. The filtrate is then concentrated until a precipitate isobtained. The solid is filtered, washed with isopropanol and then driedunder vacuum in the presence of potassium hydroxide. 5.9 g (72%) of4-[4-(3-pyrrolidin-1-yl-propyl)-[1,4]diazepan-1-yl)phenylaminetrihydrochloride (2) are thus obtained in the form of a white solid.

Spectroscopic Data:

¹H NMR (D20 d6, 500 MHz): 2.02-2.04 (m, 2H), 2.18 (m, 2H), 2.18-2.31 (m,4H), 3.12-3.14 (m, 2H), 3.30-3.35 (m, 4H), 3.57-3.59 (m, 2H), 3.71-3.72(m, 2H), 3.87 (m, 2H), 6.94 (d, J=8.9 Hz, 2H), 7.32 (d, J=8.9 Hz, 2H)

Mass spectrum: spectrum in conformity with the structure.

Example 4 Synthesis of 4-[1,4]diazepan-1-yl-phenylamine, dichlorohydrate(2)

Step 1: Synthesis of 1-benzyl-4-(4-nitrophenyl)-[1,4]diazepane (1)

Fluoronitrobenzene (3.09 g, 21.9 mmol) is dissolved in water (14 ml),and then potassium carbonate (3.64 g, 26.28 mmol) and1-benzylhomopiperazine (5 g, 26.28 mmol) are added. The medium is heatedat 90° C. for 4 h 20 min and then cooled to room temperature. Theprecipitate formed is filtered, and a yellow solid is obtained. 6.30 g(92.5%) of product are recovered.

Spectroscopic Data

¹H NMR (DMSO d6, 500 MHz): 2.08-2.16 (m, 2H), 2.74-2.80 (m, 2H),2.92-2.97 (m, 2H), 3.85-3.92 (m, 6H), 7.07 (d, J=9.5 Hz, 2H), 7.44-7.59(m, 5H), 8.27 (d, J=9.5 Hz, 2H)

Step 2: Synthesis of 4-[1,4]diazepan-1-yl-phenylamine, dihydrochloride(2)

In a stainless steel hydrogenating reactor, 6.3 g of1-benzyl-4-(4-nitrophenyl)-(1,4]diazepane 1 (22.26 mmol) are partiallydissolved in 170 ml of ethanol. 2.3 g of 5% Pd/C (50% moist) are added,the reactor is closed and purged with nitrogen 3 times, with stirring(1800 rpm). Hydrogen is then introduced at a pressure of 11 bar, themedium is heated to a temperature of 60° C. and then allowed to cool for3.5 hours. The reactor is then purged with nitrogen and the reactionmedium is filtered under a nitrogen atmosphere and the filtrate isimmediately recovered in a solution containing 7.6 ml of 37%hydrochloric acid and 30 ml of isopropanol. The filtrate is thenconcentrated until a precipitate is obtained. The solid is filtered,washed with isopropanol and then dried under vacuum in the presence ofpotassium hydroxide. 4.6 g of 4-[1,4]diazepan-1-yl-phenylamine,dihydrochloride (2) are thus obtained in the form of a white solid.

Spectroscopic Data:

¹H NMR (D20, 500 MHz): 2.23-2.28 (m, 2H), 3.36-3.39 (m, 2H), 3.52-3.54(m, 2H), 3.65-3.69 (m, 2H), 3.89-3.91 (m, 2H), 7.07 (m, 2H), 7.37 (m,2H)

Mass spectrum: spectrum in conformity with the structure.

Example 5 Synthesis of 2-[4-(4-aminophenyl)-[1,4]diazepan-1-yl]ethanol,dihydrochloride (2)

Step 1: Synthesis of 2-[4-(4-nitrophenyl)-[1,4]diazepan-1-yl]ethanol (1)

Fluoronitrobenzene (2.03 g, 14.4 mmol) is dissolved in water (10 ml),and then potassium carbonate (2.4 g, 17.3 mmol) and1-(2-hydroxyethyl)-homopiperazine are added. The medium is heated at 95°C. for 4 hours and then cooled to room temperature and filtered. A darkorange-coloured powder is recovered which is placed in the oven (3.5 g,yield=91.7%).

Spectroscopic Data

¹H NMR (DMSO d6, 200 MHz): 1.66-1.78 (m, 2H), 2.37-2.48 (m, 6H),2.63-2.68 (m, 2H), 3.29-3.35 (m, 2H), 3.44-3.69 (m, 4H), 4.26 (m, 1H),6.66-6.74 (m, 2H), 7.86-7.95 (m, 2H)

Step 2: Synthesis of 2-[4-(4-aminophenyl)-[1,4]diazepan-1-yl]ethanol,dihydrochloride (2)

In a stainless steel hydrogenating reactor, 6.9 g of2-[4-(4-nitrophenyl)-[1,4]diazepan-1-yl]ethanol (26.04 mmol) arepartially dissolved in 350 ml of ethanol. 2.5 g of 5% Pd/C (50% moist)are added, the reactor is closed and purged with nitrogen 3 times, withstirring (1800 rpm). Hydrogen is then introduced at a pressure of 9 barfor 4.5 hours. The reactor is then purged with nitrogen and the reactionmedium is filtered under a nitrogen atmosphere and the filtrate isimmediately recovered in a solution containing 9.8 ml of 37%hydrochloric acid and 40 ml of isopropanol. The filtrate is thenconcentrated until a precipitate is obtained. The solid is filtered,washed with isopropanol and then dried under vacuum in the presence ofpotassium hydroxide. 7.8 g of2-[4-(4-aminophenyl)-[1,4]diazepan-1-yl]ethanol, dihydrochloride (2) arethus obtained in the form of a white solid.

Spectroscopic Data:

¹H NMR (D20 d6, 500 MHz): 2.17-2.18 (m, 1H), 2.49-2.50 (m, 1H),3.10-3.21 (m, 4H), 3.41-3.55 (m, 4H), 3.78-3.81 (m, 4H), 6.83 (m, 2H),7.22 (m, 2H)

Mass spectrum: spectrum in conformity with the structure.

Elemental analysis

% C % H % N % O % Cl Theory 50.66 7.52 13.63 5.19 23 Found 50.17 7.5313.59 5.49 22.99

EXAMPLES OF COMPOSITIONS

The following compositions were prepared (content of the bases andcouplers in mol)

Examples 6 7 8 9 10 11 12 4-[1,4]Diazepan-1-yl-2- 3 × 10⁻³ 3 × 10⁻³ 3 ×10⁻³ 3 × 10⁻³ — — — methylphenylamine, trihydrochloride4-[4-(3-Pyrrolidin-1-yl- — — — — 3 × 10⁻³ 3 × 10⁻³ 3 × 10⁻³propyl)-[1,4]diazepan- 1-yl]phenylamine, trihydrochloride1,3-Dihydroxybenzene — 3 × 10⁻³ — — 3 × 10⁻³ — —1-β-Hydroxyethyloxy-2,4- — — 3 × 10⁻³ — — 3 × 10⁻³ — diaminobenzene,2HCl 2-Methyl-5-aminophenol — — — 3 × 10⁻³ — — 3 × 10⁻³ Dye carrier (*)(*) (*) (*) (*) (*) (*) Demineralized water qs 100 g 100 g 100 g 100 g100 g 100 g 100 g Examples 13 14 15 16 17 18 19 20 4-[1,4]Diazepan-1-yl-3 × 10⁻³ 3 × 10⁻³ 3 × 10⁻³ 3 × 10⁻³ — — — — phenylamine, dihydrochloride2-[4-(4-Aminophenyl)- — — — — 3 × 10⁻³ 3 × 10⁻³ 3 × 10⁻³ 3 × 10⁻³[1,4]diazepan- 1-yl]ethanol, trihydrochloride 1,3-Dihydroxybenzene — 3 ×10⁻³ — — — 3 × 10⁻³ — — 1-β-Hydroxyethyloxy- — — 3 × 10⁻³ — — — 3 × 10⁻³— 2,4-diaminobenzene, 2HCl 2-Methyl-5-aminophenol — — — 3 × 10⁻³ — — — 3× 10⁻³ Dye carrier (*) (*) (*) (*) (*) (*) (*) (*) Demineralized waterqs 100 g 100 g 100 g 100 g 100 g 100 g 100 g 100 g (*) Common dyecarrier: Polyglycerolated oleyl alcohol  4.0 g containing 2 mol ofglycerol Polyglycerolated oleyl alcohol  5.69 g A.S. containing 4 mol ofglycerol, containing 78% of active substances (A.S.) Oleic acid  3.0 gOleyl amine containing 2 mol of ethylene  7.0 g oxide, sold under thetrade name ETHOMEEN O12 by the company AKZO Diethylaminopropyllaurylamino  3.0 g A.S. succinamate, sodium salt containing 55% of A.S.Oleyl alcohol  5.0 g Oleic acid diethanolamide  12.0 g Propylene glycol 3.5 g Ethyl alcohol  7.0 g Dipropylene glycol  0.5 g Propylene glycolmonomethyl ether  9.0 g Sodium metabisulfite as an aqueous 0.455 g A.S.solution containing 35% of A.S. Ammonium acetate  0.8 g Antioxidant,sequestrant q.s. Perfume, preservative q.s. Aqueous ammonia containing20% of NH₃  10.0 g

At the time of use, each composition is mixed with an equal weight ofhydrogen peroxide at 20 volumes (6% by weight).

Each mixture obtained is applied to locks of natural or permanentlywaved grey hair which is 90% white. After leaving for 30 min, the locksare rinsed, washed with a standard shampoo, rinsed again and then dried.

The colour of the locks was evaluated in the L*a*b* system by means of aMINOLTA CM 2002 spectrophotometer.

In the L*a*b* space, the clarity is indicated by the value L* on a scalefrom 0 to 100 whereas the chromatic coordinates are expressed by a* andb* which indicate two colour axes, a* the green-red axis and b* theblue-yellow axis.

According to this system, the higher the value of L, the lighter andless intense the colour. Conversely, the lower the value of L, thedarker or more intense the colour.

The results are presented in Table 1 below.

TABLE 1 Nature of Examples the locks L* a* b* Ref. 1 natural 61.06 0.7211.74 Ref. 2 permanently 59.7 0.24 9.10 waved  6 natural 50.38 3.45 7.46 7 natural 38.86 5.30 5.97  8 natural 28.26 −0.41 −12.60  9 natural32.71 10.85 −7.57 10 natural 32.01 5.87 3.38 11 natural 27.47 −0.98−11.14 12 natural 33.39 8.39 −7.77 13 natural 55.66 4.21 10.12 14natural 49.12 3.93 9.59 15 natural 39.85 −5.27 −0.29 16 natural 45.92−0.57 −3.41 17 natural 39.97 1.53 5.77 permanently 33.47 2.56 5.98 waved18 natural 30.79 5.35 4.86 permanently 25.74 4.60 3.94 waved 19 natural22.04 2.19 −10.60 permanently 20.04 1.67 −5.66 waved 20 natural 25.159.51 −5.83 permanently 20.50 6.67 −4.54 waved

1. A composition for the oxidation dyeing of keratin fibers comprising:a medium suitable for dyeing, and at least one oxidation base comprisedin said medium and chosen from compounds of the following formula (I)and the addition salts thereof:

wherein: R₁ is chosen from: a halogen atom; and linear and branchedC₁-C₆ hydrocarbon chains, wherein the hydrocarbon chains may besaturated or may comprise at least one bond chosen from double bonds andtriple bonds, the hydrocarbon chains may form at least one ring chosenfrom 3- to 6-membered rings, wherein at least one carbon atom can bereplaced by at least one entity chosen from oxygen, nitrogen and sulphuratoms, and an SO₂ group, or, when the carbon is terminal, it may bereplaced by a halogen atom; provided that the radical R₁ does notcomprise a peroxide bond, a diazo radical, a nitro radical, or a nitrosoradical; n is a number ranging from 0 to 4 inclusive, it beingunderstood that when n is greater than or equal to 2, then the radicalsR₁ may be identical or different; R₂ is chosen from: a hydrogen atom;alkyl radicals which may be unsaturated, unsubstituted and substitutedwith at least one radical chosen from carboxyl radicals, alkylcarbonylradicals, alkoxycarbonyl radicals, carbamoyl radicals, mono- anddialkylcarbamoyl radicals, saturated and unsaturated, nitrogen-oxygen-and sulphur-comprising heterocyclic radicals comprising 4, 5, 6 or 7,identical or different, atoms; alkyl radicals which may be unsaturated,substituted at least at the 2-position by at least one radical chosenfrom hydroxyl radicals, alkoxy radicals, amino radicals, mono- anddialkylamino radicals, thiol radicals and halogen atoms; analkylcarbonyl radical; an alkoxycarbonyl radical; a monoalkylcarbamoyland dialkylcarbamoyl radical; a carbamoyl radical; and a radicalR₆R₇N—C═NR₅— wherein R₅, R₆, and R₇, which may be identical ordifferent, are each chosen from hydrogen, C₁-C₄ alkyl radicals andhydroxyalkyl radicals; R₃ is chosen from: a hydrogen atom; alkylradicals which may be unsaturated; a hydroxyl radical; a hydroxyalkylradical; an alkoxy radical; an alkoxyalkyl radical; an alkylcarbonylradical; a hydroxyalkoxyalkyl radical; an amino radical; amonoalkylamino and a dialkylamino radical; an aminoalkyl radical, itbeing possible for the amine to be mono- or disubstituted with at leastone identical or different radical chosen from alkyl, acetyl andhydroxyalkyl radicals; a hydroxy- and aminoalkyl radical; a carboxylradical; a carboxyalkyl radical; a carbamoyl radical; a carbamoylalkylradical; an alkoxycarbonyl radical; and a monoalkylaminocarbonyl and adialkylaminocarbonyl radical; R₄ is chosen from: alkyl radicals whichmay be unsaturated; a hydroxyalkyl radical; an alkoxyalkyl radical; analkylcarbonyl radical; a hydroxyalkoxyalkyl radical; an aminoalkylradical, wherein the amine may be mono- or disubstituted with at leastone identical or different radical chosen from alkyl, acetyl andhydroxyalkyl radicals; a hydroxy- and aminoalkyl radical; a carboxylradical; a carboxyalkyl radical; a carbamoyl radical; a carbamoylalkylradical; an alkoxycarbonyl radical; and a monoalkylaminocarbonyl and adialkylaminocarbonyl radical; and m is a number ranging from 0 to 4inclusive, it being understood that when m is greater than or equal to2, then the radicals R₄ may be identical or different; wherein said atleast one oxidation base is present in said composition in an amounteffective to dye keratin fibers.
 2. The composition according to claim1, wherein, in R_(1,) the halogen atom is chosen from chlorine andbromine.
 3. The composition according to claim 1, wherein R₂ is radicalR₆R₇N—C═NR₅—, wherein R₅ is a hydrogen atom and R₆ and R₇, which may beidentical or different, are each chosen from a hydrogen atom and amethyl radical.
 4. The composition according to claim 1, wherein R₁ ischosen from alkyl, hydroxyalkyl, aminoalkyl, alkoxy, and hydroxyalkoxyradicals.
 5. The composition according to claim 1, wherein R₁ is chosenfrom methyl, hydroxymethyl, 2-hydroxyethyl, 1,2-dihydroxyethyl, methoxy,and 2-hydroxyethoxy radicals.
 6. The composition according to claim 1,wherein n is equal to 0 or
 1. 7. The composition according to claim 1,wherein R₂ is chosen from hydrogen, alkyl radicals, alkyl radicalssubstituted with at least one entity chosen from saturated andunsaturated, nitrogen-, sulfur-, and oxygen-comprising heterocyclicradicals comprising 4, 5 or 6, identical or different atoms, analkoxycarbonyl radical, and alkyl radicals substituted at least at the2-position with at least one hydroxyl radical.
 8. The compositionaccording to claim 1, wherein R₂ is chosen from a 2-hydroxyethylradical, a 3-(1-pyrrolidinyl)propyl radical, a methyl radical, an acetylradical, and hydrogen.
 9. The composition according to claim 1, whereinR₃ is chosen from hydrogen, alkyl radicals, alkyl radicals substitutedwith at least one hydroxyl radical, alkyl radicals substituted with atleast one amino radical, and carboxyl radicals.
 10. The compositionaccording to claim 1, wherein R₃ is chosen from a hydrogen atom,hydroxyl radicals, carboxyl radicals, amino radicals, hydroxymethylradicals, and aminomethyl radicals.
 11. The composition according toclaim 1, wherein R₄ is chosen from hydrogen, alkyl radicals, alkylradicals substituted with at least one hydroxyl radical, alkyl radicalssubstituted with at least one amino radical, and carboxyl radicals. 12.The composition according to claim 1, wherein R₄ is a hydrogen atom. 13.The composition according to claim 1, wherein the at least one oxidationbase of formula (I) is chosen from:4-(4-Methyl-[1,4]diazepan-1-yl)phenylamine;4-[1,4]Diazepan-1-yl-phenylamine;4-[4-(3-Pyrrolidin-1-yl-propyl)-[1,4]diazepan-1-yl]phenylamine;2-[4-(4-Aminophenyl)-[1,4]diazepan-1-yl]ethanol;1-[4-(4-Aminophenyl)-[1,4]diazepan-1-yl]ethanone;4-(4-Aminophenyl)-[1,4]diazepane-1-carboxamidine;4-(4-Aminophenyl)-N,N-dimethyl-[1,4]diazepane-1-carboxamidine;1-(4-Aminophenyl)-4-methyl-[1,4]diazepan-6-ol; 1-(4-Aminophenyl)-4-methyl-[1,4]diazepan-6-ylamine;1-(4-Aminophenyl)-4-(3-pyrrolidin-1-yl-propyl)-[1,4]diazepan-6-ol;1-(4-Aminophenyl)-4-(3-pyrrolidin-1-yl-propyl)-[1,4]diazepan-6-ylamine;1-(4-Aminophenyl)-4-(2-hydroxyethyl)-[1,4]diazepan-6-ol;2-[6-Amino-4-(4-aminophenyl)-[1,4]diazepan-1-yl]ethanol;2-[4-(4-Aminophenyl )-6-hydroxymethyl-[1,4]diazepan-1-yl]ethanol;2-Methyl-4-(4-methyl-[1,4]diazepan-1-yl)phenylamine;4-[1,4]Diazepan-1-yl-2-methylphenylamine;2-Methyl-4-[4-(3-pyrrolidin-1-yl-propyl)-[1,4]diazepan-1-yl]phenylamine;2-[4-(4-Amino-3-methylphenyl)-[1,4]diazepan-1-yl]ethanol;1-[4-(4-Amino-3-methylphenyl)-[1,4]diazepan-1-yl]ethanone;4-(4-Amino-3-methylphenyl )-[1,4]diazepane-1-carboxamidine;4-(4-Amino-3-methylphenyl )-N,N-dimethyl-[1,4]diazepane-1-carboxamidine;1-(4-Amino-3-methylphenyl)-4-methyl-[1,4]diazepan-6-ol;1-(4-Amino-3-methylphenyl)-4-methyl-[1,4]diazepan-6-ylamine;1-(4-Amino-3-methylphenyl)-4-(3-pyrrolidin-1-yl-propyl)-[1,4]diazepan-6-ol;1-(4-Amino-3-methylphenyl)-4-(3-pyrrolidin-1-yl-propyl)-[1,4]diazepan-6-ylamine;1-(4-Amino-3-methylphenyl)-4-(2-hydroxyethyl)-[1,4]diazepan-6-ol;2-[6-Amino-4-(4-amino-3-methylphenyl)-[1,4]diazepan-1-yl]ethanol; and2-[4-(4-Amino-3-methylphenyl)-6-hydroxymethyl-[1,4]diazepan-1-yl]ethanol.
 14. The compositionaccording to claim 1, wherein the at least one oxidation base of formula(I) is present in an amount ranging from 0.001% to 10% by weight,relative to the weight of the composition.
 15. The composition accordingto claim 14, wherein the at least one oxidation base of formula (I) ispresent in an amount ranging from 0.005% to 6% by weight, relative tothe total weight of the composition.
 16. The composition according toclaim 1, further comprising at least one coupler chosen frommeta-phenylenediamines, meta-aminophenols, meta-diphenols, naphthalenecouplers, heterocyclic couplers and the addition salts thereof.
 17. Thecomposition according to claim 1, further comprising at least oneadditional oxidation base chosen from para-phenylenediamines,bisphenylalkylenediamines, para-aminophenols, ortho-aminophenols,heterocyclic bases, and the addition salts thereof.
 18. The compositionaccording to claim 1, further comprising at least one direct dye.
 19. Amethod for the oxidation dyeing of keratin fibers comprising, applyingto the fibers at least one dyeing composition comprising, in a mediumsuitable for dyeing, at least one oxidation base chosen from compoundsof the following formula (I) and the addition salts thereof:

wherein: R₁ is chosen from: a halogen atom; and linear and branchedC₁-C₆ hydrocarbon chains, wherein the hydrocarbon chains may besaturated or may comprise at least one bond chosen from double bonds andtriple bonds, the hydrocarbon chains may form at least one ring chosenfrom 3- to 6-membered rings, wherein at least one carbon atom can bereplaced by at least one entity chosen from oxygen, nitrogen and sulphuratoms, and an SO₂ group, or, when the carbon is terminal, it may bereplaced by a halogen atom; provided that the radical R₁ does notcomprise a peroxide bond, a diazo radical, a nitro radical, or a nitrosoradical; n is a number ranging from 0 to 4 inclusive, it beingunderstood that when n is greater than or equal to 2, then the radicalsR₁ may be identical or different; R₂ is chosen from: a hydrogen atom;alkyl radicals which may be unsaturated, unsubstituted and substitutedwith at least one radical chosen from carboxyl radicals, alkylcarbonylradicals, alkoxycarbonyl radicals, carbamoyl radicals, mono- anddialkylcarbamoyl radicals, saturated and unsaturated, nitrogen-oxygen-and sulphur-comprising heterocyclic radicals comprising 4, 5, 6 or 7,identical or different, atoms; alkyl radicals which may be unsaturated,substituted at least at the 2-position by at least one radical chosenfrom hydroxyl radicals, alkoxy radicals, amino radicals, mono- anddialkylamino radicals, thiol radicals and halogen atoms; analkylcarbonyl radical; an alkoxycarbonyl radical; a monoalkylcarbamoyland dialkylcarbamoyl radical; a carbamoyl radical; and a radicalR₆R₇N—C═NR₅— wherein R₅, R₆, and R₇, which may be identical ordifferent, are each chosen from hydrogen, C₁-C₄ alkyl radicals andhydroxyalkyl radicals; R₃ is chosen from: a hydrogen atom; alkylradicals which may be unsaturated; a hydroxyl radical; a hydroxyalkylradical; an alkoxy radical; an alkoxyalkyl radical; an alkylcarbonylradical; a hydroxyalkoxyalkyl radical; an amino radical; amonoalkylamino and a dialkylamino radical; an aminoalkyl radical, itbeing possible for the amine to be mono- and disubstituted with at leastone identical or different radical chosen from alkyl, acetyl andhydroxyalkyl radicals; a hydroxy- and aminoalkyl radical; a carboxylradical; a carboxyalkyl radical; a carbamoyl radical; a carbamoylalkylradical; an alkoxycarbonyl radical; and a monoalkylaminocarbonyl and adialkylaminocarbonyl radical; R₄ is chosen from: alkyl radicals whichmay be unsaturated; a hydroxyalkyl radical; an alkoxyalkyl radical; analkylcarbonyl radical; a hydroxyalkoxyalkyl radical; an aminoalkylradical, wherein the amine may be mono- or disubstituted with at leastone identical or different radical chosen from alkyl, acetyl andhydroxyalkyl radicals; a hydroxy- and aminoalkyl radical; a carboxylradical; a carboxyalkyl radical; a carbamoyl radical; a carbamoylalkylradical; an alkoxycarbonyl radical; and a monoalkylaminocarbonyl and adialkylaminocarbonyl radical; and m is a number ranging from 0 to 4inclusive, it being understood that when m is greater than or equal to2, then the radicals R₄ may be identical or different/and developing thecolor with the aid of at least one oxidizing agent.
 20. The methodaccording to claim 19, wherein the at least one oxidizing agent ischosen from hydrogen peroxide, urea peroxide, alkali metal bromates,persalts, peracids and oxidase enzymes.
 21. The method according toclaim 19, wherein the at least one oxidizing agent is mixed at the timeof use with the at least one dyeing composition.
 22. The methodaccording to claim 19, wherein the at least one oxidizing agent isapplied in the form of at least one oxidizing composition simultaneouslyto or sequentially with the at least one dyeing composition to thefibers.
 23. A multicompartment device or kit comprising, at least onefirst compartment comprising at least one dyeing composition comprising,in a medium suitable for dyeing, at least one oxidation base chosen fromcompounds of the following formula (I) and the addition salts thereof:

wherein: R₁ is chosen from: a halogen atom; and linear and branchedC₁-C₆ hydrocarbon chains, wherein the hydrocarbon chains may besaturated or may comprise at least one bond chosen from double bonds andtriple bonds, the hydrocarbon chains may form at least one ring chosenfrom 3- to 6-membered rings, wherein at least one carbon atom can bereplaced by at least one entity chosen from oxygen, nitrogen and sulphuratoms, and an SO₂ group, or, when the carbon is terminal, it may bereplaced by a halogen atom; provided that the radical R₁ does notcomprise a peroxide bond, a diazo radical, a nitro radical, or a nitrosoradical; n is a number ranging from 0 to 4 inclusive, it beingunderstood that when n is greater than or equal to 2, then the radicalsR₁ may be identical or different; R₂ is chosen from: a hydrogen atom;alkyl radicals which may be unsaturated, unsubstituted and substitutedwith at least one radical chosen from carboxyl radicals, alkylcarbonylradicals, alkoxycarbonyl radicals, carbamoyl radicals, mono- anddialkylcarbamoyl radicals, saturated and unsaturated, nitrogen-oxygen-and sulphur-comprising heterocyclic radicals comprising 4, 5, 6 or 7,identical or different, atoms; alkyl radicals which may be unsaturated,substituted at least at the 2-position by at least one radical chosenfrom hydroxyl radicals, alkoxy radicals, amino radicals, mono- anddialkylamino radicals, thiol radicals and halogen atoms; analkylcarbonyl radical; an alkoxycarbonyl radical; a monoalkylcarbamoyland dialkylcarbamoyl radical; a carbamoyl radical; and a radicalR₆R₇N—C═NR₅— wherein R₅, R₆, and R₇, which may be identical ordifferent, are each chosen from hydrogen, C₁-C₄ alkyl radicals andhydroxyalkyl radicals; R₃ is chosen from: a hydrogen atom; alkylradicals which may be unsaturated; a hydroxyl radical; a hydroxyalkylradical; an alkoxy radical; an alkoxyalkyl radical; an alkylcarbonylradical; a hydroxyalkoxyalkyl radical; an amino radical; amonoalkylamino and a dialkylamino radical; an aminoalkyl radical, itbeing possible for the amine to be mono- and disubstituted with at leastone identical or different radical chosen from alkyl, acetyl andhydroxyalkyl radicals; a hydroxy- and aminoalkyl radical; a carboxylradical; a carboxyalkyl radical; a carbamoyl radical; a carbamoylalkylradical; an alkoxycarbonyl radical; and a monoalkylaminocarbonyl and adialkylaminocarbonyl radical; R₄ is chosen from: alkyl radicals whichmay be unsaturated; a hydroxyalkyl radical; an alkoxyalkyl radical; analkylcarbonyl radical; a hydroxyalkoxyalkyl radical; an aminoalkylradical, wherein the amine may be mono- or disubstituted with at leastone identical or different radical chosen from alkyl, acetyl andhydroxyalkyl radicals; a hydroxy- and aminoalkyl radical; a carboxylradical; a carboxyalkyl radical; a carbamoyl radical; a carbamoylalkylradical; an alkoxycarbonyl radical; and a monoalkylaminocarbonyl and adialkylaminocarbonyl radical; and m is a number ranging from 0 to 4inclusive, it being understood that when m is greater than or equal to2, then the radicals R₄ may be identical or different and at least onesecond compartment comprising at least one oxidizing composition.
 24. Acolored product obtained by oxidative condensation of at least onedyeing composition comprising: a medium suitable for dyeing, and atleast one oxidation base comprised in said medium and chosen fromcompounds of the following formula (I) and the addition salts thereof:

wherein: R₁ is chosen from: a halogen atom; and linear and branchedC₁-C₆ hydrocarbon chains, wherein the hydrocarbon chains may besaturated or may comprise at least one bond chosen from double bonds andtriple bonds, the hydrocarbon chains may form at least one ring chosenfrom 3- to 6-membered rings, wherein at least one carbon atom can bereplaced by at least one entity chosen from oxygen, nitrogen and sulphuratoms, and an SO₂ group, or, when the carbon is terminal, it may bereplaced by a halogen atom; provided that the radical R₁ does notcomprise a peroxide bond, a diazo radical, a nitro radical, or a nitrosoradical; n is a number ranging from 0 to 4 inclusive, it beingunderstood that when n is greater than or equal to 2, then the radicalsR₁ may be identical or different; R₂ is chosen from: a hydrogen atom;alkyl radicals which may be unsaturated, unsubstituted and substitutedwith at least one radical chosen from carboxyl radicals, alkylcarbonylradicals, alkoxycarbonyl radicals, carbamoyl radicals, mono- anddialkylcarbamoyl radicals, saturated and unsaturated, nitrogen-oxygen-and sulphur-comprising heterocyclic radicals comprising 4, 5, 6 or 7,identical or different, atoms; alkyl radicals which may be unsaturated,substituted at least at the 2-position by at least one radical chosenfrom hydroxyl radicals, alkoxy radicals, amino radicals, mono- anddialkylamino radicals, thiol radicals and halogen atoms; analkylcarbonyl radical; an alkoxycarbonyl radical; a monoalkylcarbamoyland dialkylcarbamoyl radical; a carbamoyl radical; and a radicalR₆R₇N—C═NR₅— wherein R₅, R₆, and R₇, which may be identical ordifferent, are each chosen from hydrogen, C₁-C₄ alkyl radicals andhydroxyalkyl radicals; R₃ is chosen from: a hydrogen atom; alkylradicals which may be unsaturated; a hydroxyl radical; a hydroxyalkylradical; an alkoxy radical; an alkoxyalkyl radical; an alkylcarbonylradical; a hydroxyalkoxyalkyl radical; an amino radical; amonoalkylamino and a dialkylamino radical; an aminoalkyl radical, itbeing possible for the amine to be mono- and disubstituted with at leastone identical or different radical chosen from alkyl, acetyl andhydroxyalkyl radicals; a hydroxy- and aminoalkyl radical; a carboxylradical; a carboxyalkyl radical; a carbamoyl radical; a carbamoylalkylradical; an alkoxycarbonyl radical; and a monoalkylaminocarbonyl and adialkylaminocarbonyl radical; R₄ is chosen from: alkyl radicals whichmay be unsaturated; a hydroxyalkyl radical; an alkoxyalkyl radical; analkylcarbonyl radical; a hydroxyalkoxyalkyl radical; an aminoalkylradical, wherein the amine may be mono- or disubstituted with at leastone identical or different radical chosen from alkyl, acetyl andhydroxyalkyl radicals; a hydroxy- and aminoalkyl radical; a carboxylradical; a carboxyalkyl radical; a carbamoyl radical; a carbamoylalkylradical; an alkoxycarbonyl radical; and a monoalkylaminocarbonyl and adialkylaminocarbonyl radical; and m is a number ranging from 0 to 4inclusive, it being understood that when m is greater than or equal to2, then the radicals R₄ may be identical or different; wherein said atleast one oxidation base is present in said composition in an amounteffective to dye keratin fibers.
 25. A para-phenylenediamine derivativeof formula (I) and the addition salts thereof:

wherein: R₁ is chosen from: a halogen atom; and linear and branchedC₁-C₆ hydrocarbon chains, wherein the hydrocarbon chains may besaturated or may comprise at least one bond chosen from double bonds andtriple bonds, the hydrocarbon chains may form at least one ring chosenfrom 3- to 6-membered rings, wherein at least one carbon atom can bereplaced by at least one entity chosen from oxygen, nitrogen and sulphuratoms, and an SO₂ group, or, when the carbon is terminal, it may bereplaced by a halogen atom; provided that the radical R₁ does notcomprise a peroxide bond, a diazo radical, a nitro radical, or a nitrosoradical; n is a number ranging from 0 to 4 inclusive, it beingunderstood that when n is greater than or equal to 2, then the radicalsR₁ may be identical or different; R₂ is chosen from: a hydrogen atom;alkyl radicals which may be unsaturated, unsubstituted and substitutedwith at least one radical chosen from carboxyl radicals, alkylcarbonylradicals, alkoxycarbonyl radicals, carbamoyl radicals, mono- anddialkylcarbamoyl radicals, saturated and unsaturated, nitrogen- oxygen-and sulphur-comprising heterocyclic radicals comprising 4, 5, 6 or 7,identical or different, atoms; alkyl radicals which may be unsaturated,substituted at least at the 2-position by at least one radical chosenfrom hydroxyl radicals, alkoxy radicals, amino radicals, mono- anddialkylamino radicals, thiol radicals and halogen atoms; analkylcarbonyl radical; an alkoxycarbonyl radical; a monoalkylcarbamoyland dialkylcarbamoyl radical; a carbamoyl radical; and a radicalR₆R₇N—C═NR₅— wherein R₅, R₆, and R₇, which may be identical ordifferent, are each chosen from hydrogen, C₁-C₄ alkyl radicals andhydroxyalkyl radicals; R₃ is chosen from: a hydrogen atom; alkylradicals which may be unsaturated; a hydroxyl radical; a hydroxyalkylradical; an alkoxy radical; an alkoxyalkyl radical; an alkylcarbonylradical; a hydroxyalkoxyalkyl radical; an amino radical; amonoalkylamino and a dialkylamino radical; an aminoalkyl radical, itbeing possible for the amine to be mono- and disubstituted with at leastone identical or different radical chosen from alkyl, acetyl andhydroxyalkyl radicals; a hydroxy- and aminoalkyl radical; a carboxylradical; a carboxyalkyl radical; a carbamoyl radical; a carbamoylalkylradical; an alkoxycarbonyl radical; and a monoalkylaminocarbonyl and adialkylaminocarbonyl radical; R₄ is chosen from: alkyl radicals whichmay be unsaturated; a hydroxyalkyl radical; an alkoxyalkyl radical; analkylcarbonyl radical; a hydroxyalkoxyalkyl radical; an aminoalkylradical, wherein the amine may be mono- or disubstituted with at leastone identical or different radical chosen from alkyl, acetyl andhydroxyalkyl radicals; a hydroxy- and aminoalkyl radical; a carboxylradical; a carboxyalkyl radical; a carbamoyl radical; a carbamoylalkylradical; an alkoxycarbonyl radical; and a monoalkylaminocarbonyl and adialkylaminocarbonyl radical; and m is a number ranging from 0 to 4inclusive, it being understood that when m is greater than or equal to2, then the radicals R₄ may be identical or different, wherein saidpara-phenylenediamine derivative is not4-(4-methyl-[1,4]diazepan-1-yl)phenylamine,4-(4-methyl-1,4-diazacycloheptane-1-yl)aniline,3-cyano-4-(4-t-butoxycarbonyl-1,4-cyclodiazacycloheptane)aniline,4-(4-butoxycarbonyl-1,4-diazacycloheptane)aniline.